Medical mask with a functional material

ABSTRACT

The purpose of the invention is to provide a surgical mask with sufficient antibacterial properties, by uniformly manifesting on the surface of nanofibers a functional material with antibacterial and antiviral properties. The problem is solved by a mask with a functional material which comprises a nanofiber containing at least one base polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinyl chloride, polyurethane, polyester, zein, collagen and methoxymethylated nylon, and at least one functional substance selected from a group consisting of catechin polyphenols, persimmon tannin polyphenols, grape seed polyphenols, soybean polyphenols, lemon peel polyphenols, coffee polyphenols, phenylcarboxylic acid, ellagic acid and coumalin, and having a diameter of 1 nm to 2000 nm.

TECHNICAL FIELD

The invention relates to a medical mask with a functional material.

BACKGROUND ART

Techniques for manufacturing a nanometer sized polymer fiber by anelectrospinning method have been known (Patent Literature 1). In thetechniques, a polymer solution is released from a nozzle installed onthe tip of a container in which the polymer solution as a raw materialaccumulates to a target electrode to which a high voltage is applied,thereby the polymer solution transfers from the nozzle to the targetelectrode, during that time, it becomes fibrous fibers along the line ofelectric force to manufacture the polymer fibers on the targetelectrode. This method allows manufacture of ten to several hundredsnanometer-ordered fibers or a sheet or a mat composed by gathering thefibers (nano fiver assembly).

A polymeric nanofiber manufactured by the electrospinning method has asmooth surface, and it is not necessarily easy to add surficialdecorations and functions. For this reason, when a substance other thana polymer is mixed in a polymer, the substance is embedded in thepolymer of the nanofiber, and it may not exert the original functions.

Meanwhile, technologies to provide a mask for protecting pollen (PatentLiterature 1), a water-soluble sheet (Patent Literature 3), a nanofibercontaining a functional material (Patent Literature 4) or the like fromfibers manufactured by electrospinning methods have been developed.

CITATION LIST Patent Literature

-   Patent Literature 1: U.S. Pat. No. 6,656,394-   Patent Literature 2: Japanese Published Unexamined Patent    Application No. 2010-274102-   Patent Literature 3: Domestic Re-Publication of PCT International    Publication No. 2009/031620-   Patent Literature 4: Japanese Published Unexamined Patent    Application No. 2008-38271

OUTLINE OF THE INVENTION Problems to be Solved by the Invention

However, in prior art (e.g. Patent Literature 4), the functionalmaterial cannot be said to be sufficiently and uniformly dispersed ordissolved in the nanofiber, and it is non-uniformly contained, thus itcould not sufficiently exert the effects of the functional material.

The invention was made in light of the above-mentioned circumstances,and the object is, for example, to provide a functional material-basedmask having sufficient antimicrobial properties by evenly expressing afunctional material having antimicrobial properties and antiviralproperties on a surface of a nanofiber.

Means for Solving the Problems

The inventors made the invention after many keen examinations. Theinvention for solving the problems are followings.

[1] A mask with a functional material which comprises a nanofibercontaining at least one base polymer selected from a group consisting ofPVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6,nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile,polyethylene terephthalate, polyvinyl chloride, polyurethane, polyester,zein, collagen and methoxymethylated nylon, and at least one functionalsubstance selected from a group consisting of catechin polyphenols,persimmon tannin polyphenols, grape seed polyphenols, soybeanpolyphenols, lemon peel polyphenols, coffee polyphenols,phenylcarboxylic acid, ellagic acid and coumalin, and having a diameterof 1 nm to 2000 nm.

[2] A mask with a functional material which comprises not only thenanofiber described in [1] but also a reinforcing nanofiber containingat least one reinforcing polymer selected from a group consisting ofPVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6,nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile,polyethylene terephthalate, polyvinyl chloride, polyester, zein,collagen and polyurethane and having a diameter of 1 nm to 2000 nm.

[3] The mask with the functional material according to [1] or [2],wherein the functional substance is uniformly dispersed or dissolved inthe base polymer.

[4] The mask with the functional material according to any one of [1] to[3] which consists of only the base polymer and the functionalsubstance.

[5] The mask with the functional material according to any one of [1] to[4], wherein a weight per unit area of the nanofiber is 0.005 g/m² to 10g/m².

[6] The mask with the functional material according to any one of [1] to[5], wherein an air-permeability is 1 cc/cm²·sec to 1000 cc/cm²·sec.

[7] The mask with the functional material according to any one of [1] to[6], wherein a resin constituting the resin composition mask isnegatively or positively electrostatically-charged and attractssurrounding substances positively or negativelyelectrostatically-charged.

[8] The mask with the functional material according to any one of [1] to[7] which is a surgical mask, wherein the resin composition mask iscomposed of a non-woven fabric and is for surgical applications.

[9] The surgical mask according to [8], wherein a trapping performancefor fine particles of 0.1 μm or larger is 99% or more.

[10] The surgical mask according to [8], wherein a trapping performancefor fine particles of 3 μm or larger is 99% or more.

[11]A manufacturing method for the mask according to any one of [1] to[10], wherein a polymer-containing solution is prepared by dissolving atleast one base polymer selected from a group consisting of PVA,polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethyleneterephthalate, polyvinylidene chloride, polyester, zein, collagen,polyvinyl chloride, methoxymethylated nylon and polyurethane in at leastone solvent selected from a solvent group consisting of water, acetone,methanol, ethanol, propanol, toluene, benzene, cyclohexane,cyclohexanone, tetrahydrofuran, dimethylsulfoxide, 1,4-dioxane, carbontetrachloride, methylene chloride, pyridine, N-methyl-2-pyrrolidone,ethylene carbonate, diethyl carbonate, propylene carbonate,acetonitrile, lactic acid, acetic acid, dimethylacetamide,dimethylformamide, dichloromethane, trichloromethane,hexafluoroisopropanol, formic acid, chloroform, formaldehyde andacetaldehyde; a functional substance-containing solution is prepared bydissolving at least one functional substance selected from a groupconsisting of catechin polyphenols, persimmon tannin polyphenols, grapeseed polyphenols, soybean polyphenols, lemon peel polyphenols, coffeepolyphenols, phenylcarboxylic acid, ellagic acid and coumalin in atleast one solvent selected from the solvent group; a mixed solution isprepared by mixing the polymer-containing solution and the functionalsubstance-containing solution; and the mask is manufactured from a fibermade by spinning this mixed solution by an electrospinning method.

[12] The manufacturing method for the mask according to [11], whereinany of the solvents for preparing the polymer-containing solution andthe functional substance-containing solution is any one selected from agroup consisting of formic acid, hexafluoroisopropanol, water,dimethylformamide, ethanol and dichloromethane.

[13] The manufacturing method for the mask according to [11] or [12],wherein the functional substance-containing solution contains sodiumchloride.

[14] The manufacturing method for the mask according to any one of [11]to [13], wherein the mixed solution is uniform in properties andtransparent.

In manufacturing the mask, a method in which when the nanofibernon-woven fabric is spun, a non-woven fabric with a diameter of 1 nm to10 cm is used as a collector to spin it on the non-woven fabric, or amethod in which only the nanofiber non-woven fabric is spun, then it isadhered to the non-woven fabric with a diameter of 1 nm to 10 cm bythermocompression bonding or an adhesive component such as a solvent,can be adopted.

Advantageous Effects of the Invention

According to the present invention, a non-woven fabric containingfunctional substances uniformly on the nanofiber can be provided. Sincethis nanofiber non-woven fabric has both functions of the nanofiber andfunctions of catechins as the functional substances, it hasantioxidative effects, antimicrobial effects, antiviral effects,deodorizing effects, harmful substance-adsorbing effects, antifungaleffects and the like. Thus, it can be preferably used for a mask withfunctional material, particularly for a surgical mask.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an electron micrograph of a nanofiber in an Example 1(magnification ratio: ×1000).

FIG. 2 is an electron micrograph of a nanofiber in an Example 1(magnification ratio: ×4000).

FIG. 3 is an electron micrograph of a nanofiber in an Example 2(magnification ratio: ×1000).

FIG. 4 is an electron micrograph of a nanofiber in an Example 2(magnification ratio: ×4000).

FIG. 5 is an electron micrograph of a nanofiber in an Example 3(magnification ratio: ×500).

FIG. 6 is an electron micrograph of a nanofiber in an Example 3(magnification ratio: ×3000).

FIG. 7 is an electron micrograph of a nanofiber in an Example 4(magnification ratio: ×1000).

FIG. 8 is an electron micrograph of a nanofiber in an Example 5(magnification ratio: ×500).

FIG. 9 is an electron micrograph of a nanofiber in an Example 5(magnification ratio: ×20000).

FIG. 10 is an electron micrograph of a nanofiber in an Example 6(magnification ratio: ×500).

FIG. 11 is an electron micrograph of a nanofiber in an Example 6(magnification ratio: ×20000).

FIG. 12 is an electron micrograph of a nanofiber in an Example 7(magnification ratio: ×10000).

FIG. 13 is an electron micrograph of a nanofiber in an Example 8(magnification ratio: ×500).

FIG. 14 is an electron micrograph of a nanofiber in an Example 8(magnification ratio: ×20000).

FIG. 15 is an electron micrograph of a nanofiber in an Example 9(magnification ratio: ×500).

FIG. 16 is an electron micrograph of a nanofiber in an Example 9(magnification ratio: ×20000).

FIG. 17 is an electron micrograph of a nanofiber in an Example 10(magnification ratio: ×5000).

FIG. 18 is an electron micrograph of a nanofiber in an Example 10(magnification ratio: ×20000).

FIG. 19 is an electron micrograph of a nanofiber in an Example 11(magnification ratio: ×500).

FIG. 20 is an electron micrograph of a nanofiber in an Example 11(magnification ratio: ×20000).

FIG. 21 is an electron micrograph of a nanofiber in an Example 12(magnification ratio: ×500).

FIG. 22 is an electron micrograph of a nanofiber in an Example 12(magnification ratio: ×20000).

FIG. 23 is an electron micrograph of a nanofiber in an Example 13(magnification ratio: ×4000).

FIG. 24 is an electron micrograph of a nanofiber in an Example 14(magnification ratio: ×5000).

FIG. 25 is an electron micrograph of a nanofiber in an Example 15(magnification ratio: ×5000).

FIG. 26 is an electron micrograph of a nanofiber in an Example 16(magnification ratio: ×5000).

FIG. 27 is an electron micrograph of a nanofiber in an Example 17(magnification ratio: ×5000).

FIG. 28 is an electron micrograph of a nanofiber in an Example 18(magnification ratio: ×20000).

FIG. 29 is an electron micrograph of a nanofiber in an Example 19(magnification ratio: ×1000).

FIG. 30 is an electron micrograph of a nanofiber in an Example 20(magnification ratio: ×1000).

FIG. 31 is an electron micrograph of a nanofiber in an Example 20(magnification ratio: ×5000).

FIG. 32 is an electron micrograph of a nanofiber in an Example 21(magnification ratio: ×5000).

FIG. 33 is an electron micrograph of a nanofiber in an Example 21(magnification ratio: ×20000).

FIG. 34 is an electron micrograph of a nanofiber in an Example 22(magnification ratio: ×5000).

FIG. 35 is an electron micrograph of a nanofiber in an Example 22(magnification ratio: ×20000).

FIG. 36 is an electron micrograph of a nanofiber in an Example 23(magnification ratio: ×5000).

FIG. 37 is an electron micrograph of a nanofiber in an Example 23(magnification ratio: ×20000).

MODES FOR CARRYING OUT THE INVENTION

Next, a detailed explanation of the embodiment of the present inventionwill be given. The technical scope of the present invention is notlimited to the following embodiments but can be performed by variousmodifications without changing the gist of the invention. In addition,the technical scope of the present invention reaches the equivalentrange.

The PVA used in the present invention means a kind of synthetic resinrepresented by a rational formula (—CH₂CH(OH)—)_(n), and has very highhydrophilicity due to the inclusion of many hydroxyl groups and issoluble in hot water.

The polylactic acid means a kind of biodegradable plastic which wasproduced as high-molecular-weight products by chaining a plurality oflactic acids (CH₃CH(OH)COOH) as a unit. The lactic acid as a materialfor manufacturing the polylactic acid can be produced from vegetables(e.g. corn, cassava, sugar cane, beet, sweet potato, etc.). Formanufacturing the polylactic acid, generally, a lactic acid is cyclizedto produce a lactide, and this is turned into the polylactic acid byring-opening polymerization, but the manufacturing method of thepolylactic acid is not particularly limited in the present invention.

It is known that the lactic acid as an elementary substance constitutingthe polylactic acid includes two types, L- and D-optical isomers. Thepresent invention can also be used for polylactic acids manufacturedusing any of L- and D-lactic acids as a unit (alternatively, forpolylactic acids comprising L- and D-lactic acids at any ratio).

The fibroin means a kind of fibrous protein which is a principalcomponent of silken threads.

The chitosan mainly means β-1,4-polyglucosamine, which is adeacetylation of chitin. Although the chitosan is mainly composed of aβ-1,4-polyglucosamine structure, its structure may be somewhat changedbecause it is manufactured by dissolving the chitin with a concentratedalkali.

The chitin means a linear nitrogen-containing polysaccharide polymercomprising a poly-β1-4-N-acetylglucosamine. It is known as a principalcomponent of the exoskeleton of arthropods and crustaceans.

Nylon 6, Nylon 66, Nylon 9T and Nylon 610 mean kinds of polyamidesynthetic fibers.

The polyamide means a polymer composed by bonding a large number ofmonomers through amide bonds.

The polystyrene means a polymer composed by bonding a large number ofstyrenes.

The polyacrylonitrile means a kind of organic polymer obtained bypolymerizing acrylonitriles.

The polyethylene terephthalate means a kind of polyester formed bydehydrocondensation of ethyleneglycol and terephthalic acid.

The polyvinyl chloride means a kind of polymeric compound obtained bypolymerization of vinyl chloride or by copolymerization with vinylacetate or the like.

The polyvinylidene chloride means a synthetic resin composed bypolymerizing vinylidene groups including chlorine.

The polyester means a polycondensate of a polyvalent carboxylic acid anda polyalcohol.

The zein is a main protein of a corn seed and belongs to prolamins. Theprolamin belongs to simple proteins, can be dissolved in a 60% to 90%ethanol and is the general term for proteins insoluble in an over 90%ethanol, water and a neutral salt solution, and other examples includegliadin of wheat, hordein of barley and the like. The zein is composedof various molecular species, and main components have molecular weightsof 22000 and 19000.

The collagen means the main protein component constituting connectivetissues in animals. In mammals, it accounts for approximately 30% of thetotal proteins in a body. The collagen comprises 10 or more kinds ofprotein superfamilies like type I and II collagens, and contains a largeamount of glycine and proline. In the present invention, any type ofcollagen or mixture can be used.

The catechin polyphenols mean water-soluble polyhydric phenols which areabundantly contained in plants such as tea. In a classification methodfor the catechins, they are classified into unpolymerized catechins andpolymerized catechins. In addition, the unpolymerized catechins includegallate types including a catechin gallate, epicatechin gallate,gallocatechin gallate and epigallocatechin gallate, and non-gallatetypes including catechin, epicatechin, gallocatechin andepigallocatechin. In further classification method, the catechins areclassified into epi types including epicatechin, epigallocatechin,epicatechin gallate and epigallocatechin gallate, and non-epi typesincluding catechin, gallocatechin, catechin gallate and gallocatechingallate.

The catechin oligomer means an oligomer composed of a plurality of, 3 to10 catechins bound to each other. Although the catechins include aplurality of types as mentioned above, any catechin oligomer to whichany molecules of them (including homogeneity or heterogeneity) are boundcan be used in the present invention.

The persimmon tannin polyphenols mean polyphenols derived from juiceobtained from fruits of astringent persimmons. The persimmon tanninpolyphenols contain tannin, catechin, flavonoid and the like.

The grape seed polyphenols mean polyphenols derived from juice obtainedfrom grape seeds. The grape seed polyphenols contain anthocyanin and thelike.

The soybean polyphenols mean polyphenols derived from sap obtained fromsoybeans. The soybean polyphenols contain isoflavone, anthocyanin andthe like.

The lemon peel polyphenols mean polyphenols derived from juice obtainedfrom lemon peel. The lemon peel polyphenols contain hesperidin and thelike.

The coffee polyphenols mean polyphenols obtained from sap of coffeebeans. The coffee polyphenols contain bitterness components like achlorogenic acid.

It should be noted that “the catechin polyphenols, persimmon tanninpolyphenols, grape seed polyphenols, soybean polyphenols, lemon peelpolyphenols, coffee polyphenols, phenylcarboxylic acid, eliagic acid andcoumalin” are collectively called “polyphenol compounds” in thespecification. In addition, the polyphenol compounds are included in thefunctional substances of the invention of the present application.

The nanofiber of the present invention means a fiber having a singleyarn diameter of about 1 nm to about 2000 nm, and when it ismanufactured by the electrospinning method, a non-woven fabric iscomposed of the nanofiber assembly. The nanofiber obtained as anon-woven fabric is effectively used as a mask, particularly as asurgical mask.

Extremely low air-permeability of the mask is unfavorable because oflabored breathing. In addition, although a mask having highair-permeability is favorable, it may lead to significant technicalproblems. For this reason, an upper limit value of the air-permeabilityis, but not particularly limited to, 1000 cc/cm²·sec or less, preferably500 cc/cm²·sec or less, more preferably 300 cc/cm²·sec or less, and alower limit value is 1 cc/cm²·sec or more, preferably 100 cc/cm²·sec ormore, more preferably 150 cc/cm²·sec or more.

For manufacturing the non-woven fabric, a base polymer is dissolved in aproper solvent (inorganic solvent such as water, acid amide-basedsolvent (including protic polar solvent, aprotic polar solvent), organicacid solvent (particularly including a solvent containing carboxylicacid or sulfonic acid)). Aside from this, a polyphenol compound isdissolved in an organic acid solvent (particularly including a solventcontaining the carboxylic acid or sulfonic acid).

For preparing a biodegradable polyester-containing solution (or apolymer-containing solution), 1 part by mass to 50 parts by mass(preferably 3 parts by mass to 20 parts by mass, more preferably 3 partsby mass to 10 parts by mass) of base polymer is dissolved in 50 parts bymass to 99 parts by mass (preferably 80 parts by mass to 97 parts bymass, more preferably 90 parts by mass to 99 parts by mass) of solvent.In addition, for preparing a functional substance-containing solution,0.001 parts by mass to 70 parts by mass (preferably 0.1 parts by mass to60 parts by mass, more preferably 1 part by mass to 50 parts by mass) offunctional substance is dissolved in 30 parts by mass to 99.999 parts bymass (preferably 40 parts by mass to 99.999 parts by mass, morepreferably 50 parts by mass to 99.999 parts by mass). Additionally, thebiodegradable polyester-containing solution (or the polymer-containingsolution) and the functional substance-containing solution are mixed ina ratio of 50 parts by mass to 99.999 parts by mass: 0.0001 parts bymass to 50 parts by mass (preferably 60 parts by mass to 99.999 parts bymass: 0.0001 parts by mass to 40 parts by mass, more preferably 75 partsby mass to 99 parts by mass: 1 part by mass to 25 parts by mass). In thenanofiber manufactured in this way, the ratio of the polymer to thefunctional substance is 50 parts by mass to 99.9999 parts by mass: 50parts by mass to 0.0001 parts by mass (preferably 60 parts by mass to99.9999 parts by mass: 40 parts by mass to 0.0001 parts by mass).

Subsequently, both solutions are mixed to prepare a mixed solution. Inthe present invention, since the mixed solution is transparent, thepolyphenol compound is also in a dissolved state (not in a suspendedstate). Thus, also when the electrospinning method is carried out, thepolyphenol compound is uniformly allocated in the nanofiber.

The functional substance-containing solution can comprise sodiumchloride (NaCl). This is preferable because a fiber with an ultrasmalldiameter can be stably made. Also, a concentration of sodium chloride ispreferably 0.001 mass % to 1 mass, more preferably 0.01 mass % to 0.1mass %.

The electrospinning method is carried out using the mixed solution. Theelectrospinning method may be affected by factors such as aconcentration of a spinning base material, a type of solvent, a diameterof a needle, an injection range, a rotating speed, a voltage and aninjection speed. The nanofiber non-woven fabric can actually bemanufactured by properly combining the factors.

As a test for evaluating trapping performances of fine particles with asize of 0.1 μm or larger, an evaluation by PFE (Particulate FiltrationEfficiency) can be made.

Also, as a test for evaluating trapping performances of fine particleswith a size of 3 μm or larger, an evaluation by BFE (BacterialFiltration Efficiency) can be made.

EXAMPLES

Next, the present invention will be detailed with reference to Examplesand Tests, but the present invention is not limited to these Examplesand Tests.

Example 1 Polylactic Acid+Catechin Polyphenol+NaCl

A polylactic acid (Mitsui Chemicals, Inc.) was used as a base polymer,and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd.,hereinafter called “catechin (Sunphenon BG-3)”) was used as a functionalsubstance to make a non-woven fabric.

10 g of polylactic acid and 90 g of dichloromethane were mixed and apolylactic acid resin was dissolved at normal temperature (about 25° C.)to prepare a biodegradable polyester-containing solution(polymer-containing solution). In addition, ethanol was added to thecatechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenolcompound-containing solution (functional substance-containing solution),in which 0.01 wt % of NaCl was further dissolved. The two solutions, 7.5g of biodegradable polyester-containing solution and 2.5 g of polyphenolcompound-containing solution were mixed to obtain a colorless andtransparent mixed solution. This mixed solution (transparent solutioncontaining the polylactic acid and catechin polyphenol) was filled intoa syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co.,Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used.Voltage of 20 KV to 50 KV was applied under atmospheric pressure at roomtemperature (about 25° C.), and electrospinning was carried out in sucha way that a distance from a inner bore on the syringe needle tip to afibrous material-collecting electrode was set to 10 cm to 200 cm, toobtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.1 and FIG. 2. An average fiber diameter of the non-woven fabric was 500nm. In addition, a fiber with a diameter of 2 μm or larger was notobserved. A weight per unit area was 0.5 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 2 Polylactic Acid+Catechin Polyphenol

A polylactic acid (Mitsui Chemicals, Inc.) was used as a base polymer,and a catechin polyphenol (Sunphenon EGCg, Taiyo Kagaku Co., Ltd.,hereinafter called “catechin (Sunphenon EGCg)”) was used as a functionalsubstance to make a non-woven fabric.

10 g of polylactic acid and 90 g of dichloromethane were mixed and apolylactic acid resin was dissolved at normal temperature (about 25° C.)to prepare a biodegradable polyester-containing solution(polymer-containing solution). In addition, dimethylformamide was addedto the catechin (Sunphenon EGCg) and dissolved to prepare a 20 wt %polyphenol compound-containing solution (functional substance-containingsolution). Of the two solutions, 7.5 g of biodegradablepolyester-containing solution and 2.5 g of polyphenolcompound-containing solution were mixed to obtain a transparent mixedsolution. This mixed solution (transparent solution containing thepolylactic acid and catechin EGCg) was filled into a syringe. As aneedle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outsidediameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KVto 50 KV was applied under atmospheric pressure at room temperature(about 25° C.), and electrospinning was carried out in such a way thatthe distance from the inner bore on the syringe needle tip to thefibrous material-collecting electrode was set to 10 cm to 200 cm, toobtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.3 and FIG. 4. An average fiber diameter of the non-woven fabric was 500nm. In addition, a fiber with a diameter of 2 μm or larger was notobserved. A weight per unit area was 0.5 g/m². In addition, the weightper unit area could be freely designed according to applications in thesame range as in the Example 1 by appropriately changing the conditions.

Example 3 Polylactic Acid+Persimmon Tannin Polyphenol

A polylactic acid (Mitsui Chemicals, Inc.) was used as a base polymer,and a persimmon tannin polyphenol (odorless persimmon tannin: Osugi Co.,ltd.) was used as a functional substance to make a non-woven fabric.

10 g of polylactic acid and 90 g of dichloromethane were mixed and apolylactic acid resin was dissolved at normal temperature (about 25° C.)to prepare a biodegradable polyester-containing solution(polymer-containing solution). In addition, dimethylformamide was addedto the persimmon tannin polyphenol and dissolved to prepare a solutioncontaining 20 wt % of polyphenol compound (functionalsubstance-containing solution). Of the two solutions, 7.5 g ofbiodegradable polyester-containing solution and 2.5 g of polyphenolcompound-containing solution were mixed to obtain a transparent mixedsolution. This mixed solution (transparent solution containing thepolylactic acid and persimmon tannin polyphenol) was filled into asyringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd.,outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of20 KV to 50 KV was applied under atmospheric pressure at roomtemperature (about 25° C.), and electrospinning was carried out in sucha way that the distance from the inner bore on the syringe needle tip tothe fibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.5 and FIG. 6. An average fiber diameter of the non-woven fabric was 2μm. The weight per unit area was 0.5 g/m². In addition, the weight perunit area could be freely designed according to applications in the samerange as in the Example 1 by appropriately changing the conditions.

Example 4 Polyvinyl Alcohol+Catechin Polyphenol

A polyvinyl alcohol (Wako Pure Chemical Industries, Ltd., hereinaftercalled “PVA”) was used as a base polymer, and a catechin polyphenol(Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin(Sunphenon BG-3)”) was used as a functional substance to make anon-woven fabric.

10 g of PVA and 90 g of ion-exchanged water were mixed and the PVA wasdissolved while heating (40° to 60° C.) to prepare a biodegradablepolyester-containing solution (polymer-containing solution). Inaddition, ethanol was added to the catechin (Sunphenon BG-3) and mixedto prepare a 20 wt % polyphenol compound-containing solution (functionalsubstance-containing solution). Of the two solutions, 7.5 g of polyvinylalcohol-containing solution and 2.5 g of polyphenol compound-containingsolution were mixed to obtain a red-brown transparent mixed solution.This mixed solution (transparent solution containing the PVA andcatechin (Sunphenon BG-3)) was filled into a syringe. As a needle for asyringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm,inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV wasapplied under atmospheric pressure at room temperature (about 25° C.),and electrospinning was carried out in such a way that the distance fromthe inner bore on the syringe needle tip to the fibrousmaterial-collecting electrode was set to 10 cm to 200 cm to obtain thenanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.7. An average fiber diameter of the non-woven fabric was 250 nm to 500nm. In addition, a fiber with a diameter of 1 μm or larger was notobserved. A weight per unit area was 0.01 g/m². In addition, the weightper unit area could be freely designed according to applications in thesame range as in the Example 1 by appropriately changing the conditions.

Example 5 Polyvinyl Chloride+Catechin Polyphenol

A polyvinyl chloride (Wako Pure Chemical Industries, Ltd.) was used as abase polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo KagakuCo., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as afunctional substance to make a non-woven fabric.

10 g of polyvinyl chloride and 90 g of dimethylformamide solution weremixed and the polyvinyl chloride was dissolved at normal temperature(about 25° C.) to prepare a polyvinyl chloride-containing solution(polymer-containing solution). In addition, ethanol was added to thecatechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenolcompound-containing solution (functional substance-containing solution).Of the two solutions, 7.5 g of polyvinyl chloride-containing solutionand 2.5 g of polyphenol compound-containing solution were mixed toobtain a brown transparent mixed solution. Next, this mixed solution(transparent solution containing the polyvinyl chloride and catechinpolyphenol) was filled into a syringe. As a needle for a syringe, a 25 Gneedle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter:0.32 mm) was used. Voltage of 20 KV to 50 KV was applied underatmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such a way that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.8 and FIG. 9. An average fiber diameter of the non-woven fabric was 150nm. In addition, a fiber with a diameter of 1 μm or larger was notobserved. A weight per unit area was 0.1 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 6 Polyethylene Terephthalate+Catechin Polyphenol

A polyethylene terephthalate was used as a base polymer, and a catechinpolyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called“catechin (Sunphenon BG-3)”) was used as a functional substance to makea non-woven fabric.

10 g of polyethylene terephtalate and 90 g of1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solution were mixed and thepolyethylene terephtalate was dissolved at normal temperature (about 25°C.) to prepare a polyethylene terephtalate-containing solution(polymer-containing solution). In addition, ethanol was added to thecatechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenolcompound-containing solution (functional substance-containing solution).Of the two solutions, 7.5 g of polyethylene terephthalate-containingsolution and 2.5 g of polyphenol compound-containing solution were mixedto obtain a brown transparent mixed solution. Next, this mixed solution(transparent solution containing the polyethylene terephthalate andcatechin polyphenol) was filled into a syringe. As a needle for asyringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm,inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV wasapplied under atmospheric pressure at room temperature (about 25° C.),and electrospinning was carried out in such a way that the distance fromthe inner bore on the syringe needle tip to the fibrousmaterial-collecting electrode was set to 10 cm to 200 cm to obtain thenanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.10 and FIG. 11. An average fiber diameter of the non-woven fabric was500 nm. In addition, a fiber with a diameter of 1 μm or larger was notobserved. A weight per unit area was 0.7 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 7 Polyurethane+Catechin Polyphenol

A polyurethane was used as a base polymer, and a catechin polyphenol(Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin(Sunphenon BG-3)”) was used as a functional substance to make anon-woven fabric.

10 g of polyurethane and 90 g of dimethylformamide solution were mixedand the polyurethane was dissolved at normal temperature (about 25° C.)to prepare a polyurethane-containing solution (polymer-containingsolution). In addition, ethanol was added to the catechin (SunphenonBG-3) and dissolved to prepare a 20 wt % polyphenol compound-containingsolution (functional substance-containing solution). Of the twosolutions, 7.5 g of polyurethane-containing solution and 2.5 g ofpolyphenol compound-containing solution were mixed to obtain a browntransparent mixed solution. Next, this mixed solution (transparentsolution containing the polyurethane and catechin polyphenol) was filledinto a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDOCo., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used.Voltage of 20 KV to 50 KV was applied under atmospheric pressure at roomtemperature (about 25° C.), and electrospinning was carried out in sucha way that the distance from the inner bore on the syringe needle tip tothe fibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.12. An average fiber diameter of the non-woven fabric was 500 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.5 g/m². In addition, the weight per unit areacould be freely designed according to applications in a range of 0.005g/m² to 10 g/m² by appropriately changing the conditions.

Example 8 Soluble Nylon (Methoxymethylated Nylon)+Catechin Polyphenol

A soluble nylon (methoxymethylated nylon) was used as a base polymer,and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd.,hereinafter called “catechin (Sunphenon BG-3)”) was used as a functionalsubstance to make a non-woven fabric.

10 g of soluble nylon and 90 g of 1,1,1,3,3,3-hexafluoroisopropanol(HFIP) solution were mixed and the soluble nylon was dissolved at normaltemperature (about 25° C.) to prepare a soluble nylon-containingsolution (polymer-containing solution). In addition, ethanol was addedto the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt,polyphenol compound-containing solution (functional substance-containingsolution). Of the two solutions, 7.5 g of soluble nylon-containingsolution and 2.5 g of polyphenol compound-containing solution were mixedto obtain a brown transparent mixed solution. Next, this mixed solution(transparent solution containing the soluble nylon and catechinpolyphenol) was filled into a syringe. As a needle for a syringe, a 25 Gneedle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter:0.32 mm) was used. Voltage of 20 KV to 50 KV was applied underatmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such a way that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.13 and FIG. 14. An average fiber diameter of the non-woven fabric was500 nm. In addition, a fiber with a diameter of 1 μm or larger was notobserved. A weight per unit area was 0.3 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 9 Polyactic Acid+Phenylcarboxylic Acid

A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer,and a phenylcarboxylic acid (gallic acid) was used as a functionalsubstance to make a non-woven fabric.

10 g of polyactic acid and 90 g of dichloromethane solution were mixedand the polyactic acid was dissolved at normal temperature (about 25°C.) to prepare a polyactic acid-containing solution (polymer-containingsolution). In addition, ethanol was added to the phenylcarboxylic acid(gallic acid) and dissolved to prepare a 20 wt* polyphenolcompound-containing solution (functional substance-containing solution).Of the two solutions, 7.5 g of polyactic acid-containing solution and2.5 g of polyphenol compound-containing solution were mixed to obtain acolorless and transparent mixed solution. Next, this mixed solution(transparent solution containing the polyactic acid and phenylcarboxylicacid) was filled into a syringe. As a needle for a syringe, a 25 Gneedle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter:0.32 mm) was used. Voltage of 20 KV to 50 KV was applied underatmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such a way that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.15 and FIG. 16. An average fiber diameter of the non-woven fabric was1000 nm. In addition, a fiber with a diameter of 2 μm or larger was notobserved. A weight per unit area was 0.5 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 10 Polyactic Acid+Ellagic Acid

A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer,and a ellagic acid was used as a functional substance to make anon-woven fabric.

10 g of polyactic acid and 90 g of dichloromethane solution were mixedand the polyactic acid was dissolved at normal temperature (about 25°C.) to prepare a polyactic acid-containing solution (polymer-containingsolution). In addition, dimethylformamide was added to the ellagic acidand dissolved to prepare a 20 wt % polyphenol compound-containingsolution (functional substance-containing solution). Of the twosolutions, 7.5 g of polyactic acid-containing solution and 2.5 g ofpolyphenol compound-containing solution were mixed to obtain a colorlessand transparent mixed solution. Next, this mixed solution (transparentsolution containing the polyactic acid and ellagic acid) was filled intoa syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co.,Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used.Voltage of 20 KV to 50 KV was applied under atmospheric pressure at roomtemperature (about 25° C.), and electrospinning was carried out in sucha way that the distance from the inner bore on the syringe needle tip tothe fibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.17 and FIG. 18. An average fiber diameter of the non-woven fabric was1500 nm. In addition, a fiber with a diameter of 2 μm or larger was notobserved. A weight per unit area was 0.5 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 11 Polyactic Acid+Coumalin

A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer,and a coumalin was used as a functional substance to make a non-wovenfabric.

10 g of polyactic acid and 90 g of dichloromethane solution were mixedand the polyactic acid was dissolved at normal temperature (about 25°C.) to prepare a polyactic acid-containing solution (polymer-containingsolution). In addition, dimethylformamide was added to the coumalin anddissolved to prepare a 20 wt % polyphenol compound-containing solution(functional substance-containing solution). Of the two solutions, 7.5 gof polyactic acid-containing solution and 2.5 g of polyphenolcompound-containing solution were mixed to obtain a colorless andtransparent mixed solution. Next, this mixed solution (transparentsolution containing the polyactic acid and coumalin) was filled into asyringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd.,outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of20 KV to 50 KV was applied under atmospheric pressure at roomtemperature (about 25° C.), and electrospinning was carried out in sucha way that the distance from the inner bore on the syringe needle tip tothe fibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.19 and FIG. 20. An average fiber diameter of the non-woven fabric was1500 nm. In addition, a fiber with a diameter of 2 μm or larger was notobserved. A weight per unit area was 0.5 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 12 Polyactic Acid+Coffee Polyphenols (Chlorogenic Acid)

A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer,and coffee polyphenols (chlorogenic acid) were used as a functionalsubstance to make a non-woven fabric.

10 g of polyactic acid and 90 g of dichloromethane solution were mixedand the polyactic acid was dissolved at normal temperature (about 25°C.) to prepare a polyactic acid-containing solution (polymer-containingsolution). In addition, dimethylformamide was added to the coffeepolyphenols (chlorogenic acid) and dissolved to prepare a 20 wt %polyphenol compound-containing solution (functional substance-containingsolution). Of the two solutions, 7.5 g of polyactic acid-containingsolution and 2.5 g of polyphenol compound-containing solution were mixedto obtain a colorless and transparent mixed solution. Next, this mixedsolution (transparent solution containing the polyactic acid and coffeepolyphenols (chlorogenic acid)) was filled into a syringe. As a needlefor a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter:0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KVwas applied under atmospheric pressure at room temperature (about 25°C.), and electrospinning was carried out in such a way that the distancefrom the inner bore on the syringe needle tip to the fibrousmaterial-collecting electrode was set to 10 cm to 200 cm to obtain thenanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.21 and FIG. 22. An average fiber diameter of the non-woven fabric was500 nm. In addition, a fiber with a diameter of 2 μm or larger was notobserved. A weight per unit area was 0.5 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 13 Polyvinyl Alcohol+Coumalin

A polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.) was used as abase polymer, and a coumalin was used as a functional substance to makea non-woven fabric.

Polyvinyl alcohol and 50 wt % of ethanol/water solution were mixed andthe polyvinyl alcohol was dissolved while heating (40° C. to 60° C.) toprepare a polyvinyl alcohol-containing solution (polymer-containingsolution). In addition, ethanol was added to coumalin and dissolved toprepare a 20 wt % polyphenol compound-containing solution (functionalsubstance-containing solution). Of the two solutions, 7.5 g of polyvinylalcohol-containing solution and 2.5 g of polyphenol compound-containingsolution were mixed to obtain a colorless and transparent mixedsolution. Next, this mixed solution (transparent solution containing thepolyvinyl alcohol and coumalin) was filled into a syringe. As a needlefor a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter:0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KVwas applied under atmospheric pressure at room temperature (about 25°C.), and electrospinning was carried out in such a way that the distancefrom the inner bore on the syringe needle tip to the fibrousmaterial-collecting electrode was set to 10 cm to 200 cm to obtain thenanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.23. An average fiber diameter of the non-woven fabric was 150 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.1 g/m². In addition, the weight per unit areacould be freely designed according to applications in a range of 0.005g/m² to 10 g/m² by appropriately changing the conditions.

Example 14 Soluble Nylon (Methoxymethylated Nylon)+Crushed Tea Leaves

A soluble nylon (methoxymethylated nylon) was used as a base polymer,and crushed tea leaves were used as a functional substance to make anon-woven fabric.

1 g to 20 g of soluble nylon and 1,1,1,3,3,3-hexafluoroisopropanol(HFIP) solution were mixed to 100 g, and the soluble nylon was dissolvedat normal temperature (about 25° C.) to prepare a solublenylon-containing solution (polymer-containing solution). In addition, 10g of crushed tea leaves were added to the polymer-containing solution.Next, this mixed solution was filled into a syringe. As a needle for asyringe, a 18 G needle (HOSHISEIDO Co., Ltd., outside diameter: 1.3 mm,inside diameter: 1.1 mm) was used. Voltage of 20 KV to 50 KV was appliedunder atmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such a way that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.24. An average fiber diameter of the non-woven fabric was 250 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.1 g/m². In addition, the weight per unit areacould be freely designed according to applications in a range of 0.005g/m² to 10 g/m² by appropriately changing the conditions.

Example 15 Soluble Nylon (Methoxymethylated Nylon)+Crushed-Extracted TeaLeaves

A soluble nylon (methoxymethylated nylon) was used as a base polymer,and crushed-extracted tea leaves (tea leaves which was extracted bywater at 80° C. three times, dried up, and crushed) were used as afunctional substance to make a non-woven fabric.

1 g to 20 g of soluble nylon and 1,1,1,3,3,3-hexafluoroisopropanol(HFIP) solution were mixed to 100 g, and the soluble nylon was dissolvedat normal temperature (about 25° C.) to prepare a solublenylon-containing solution (polymer-containing solution). In addition,0.01 g to 10 g of crushed-extracted tea leaves (tea leaves which wasextracted by water at 80° C. three times, dried up, and crushed) wereadded to the polymer-containing solution. Next, this mixed solution wasfilled into a syringe. As a needle for a syringe, a 18 G needle(HOSHISEIDO Co., Ltd., outside diameter: 1.3 mm, inside diameter: 1.1mm) was used. Voltage of 20 KV to 50 KV was applied under atmosphericpressure at room temperature (about 25° C.), and electrospinning wascarried out in such a way that the distance from the inner bore on thesyringe needle tip to the fibrous material-collecting electrode was setto 10 cm to 200 cm to obtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.25. An average fiber diameter of the non-woven fabric was 450 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.2 g/m². In addition, the weight per unit areacould be freely designed according to applications in a range of 0.005g/m² to 10 g/m² by appropriately changing the conditions.

Example 16 Polyvinyl Alcohol+Crushed Tea Leaves

A polyvinyl alcohol (Wako Pure Chemical industries, Ltd.) was used as abase polymer, and crushed tea leaves were used as a functional substanceto make a non-woven fabric.

Polyvinyl alcohol and 50 wt % of ethanol/water solution were mixed andthe polyvinyl alcohol was dissolved while heating (40° C. to 60° C.) toprepare a polyvinyl alcohol-containing solution (polymer-containingsolution). In addition, 10 g of crushed tea leaves were added to thepolymer-containing solution. Next, this mixed solution was filled into asyringe. As a needle for a syringe, a 18 G needle (HOSHISEIDO Co., Ltd.,outside diameter: 1.3 mm, inside diameter: 1.1 mm) was used. Voltage of20 KV to 50 KV was applied under atmospheric pressure at roomtemperature (about 25° C.), and electrospinning was carried out in sucha way that the distance from the inner bore on the syringe needle tip tothe fibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.26. An average fiber diameter of the non-woven fabric was 150 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.3 g/m². In addition, the weight per unit areacould be freely designed according to applications in a range of 0.005g/m² to 10 g/m² by appropriately changing the conditions.

Example 17 Polyvinyl Alcohol+Crushed-Extracted Tea Leaves

A polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.) was used as abase polymer, and crushed-extracted tea leaves (tea leaves which wasextracted by water at 80° C. three times, dried up, and crushed) wereused as a functional substance to make a non-woven fabric.

Polyvinyl alcohol and 50 wt % of ethanol/water solution were mixed andthe polyvinyl alcohol was dissolved while heating (40° C. to 60° C.) toprepare a polyvinyl alcohol-containing solution (polymer-containingsolution). In addition, 0.01 g to 10 g of crushed-extracted tea leaves(tea leaves which was extracted by water at 80° C. three times, driedup, and crushed) were added to the polymer-containing solution. Next,this mixed solution was filled into a syringe. As a needle for asyringe, a 18 G needle (HOSHISEIDO Co., Ltd., outside diameter: 1.3 mm,inside diameter: 1.1 mm) was used. Voltage of 20 KV to 50 KV was appliedunder atmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such a way that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.27. An average fiber diameter of the non-woven fabric was 150 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.3 g/m². In addition, the weight per unit areacould be freely designed according to applications in a range of 0.005g/m² to 10 g/m² by appropriately changing the conditions.

Example 18 PGA (Polyglutamic Acid)+Catechin Polyphenol

A PGA (polyglutamic acid) was used as a base polymer, and a catechinpolyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called“catechin (Sunphenon BG-3)”) was used as a functional substance to makea non-woven fabric.

PGA (polyglutamic acid) and 20 wt % to 80 wt % of ethanol/water weremixed and the PGA was dissolved while heating (40° C. to 60° C.) toprepare PGA solution. In addition, ethanol was added to the catechin(Sunphenon BG-3) and mixed to prepare a 20 wt % polyphenolcompound-containing solution. Of the two solutions, 7.5 g of PGA(polyglutamic acid)-containing solution and 2.5 g of polyphenolcompound-containing solution were mixed to obtain a mixed solution. Thismixed solution was filled into a syringe. As a needle for a syringe, a25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, insidediameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied underatmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such a way that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.28. An average fiber diameter of the non-woven fabric was 1000 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.2 g/m². In addition, the weight per unit areacould be freely designed according to applications in a range of 0.005g/m² to 10 g/m² by appropriately changing the conditions.

Example 19 Zein+Catechin Polyphenol

A zein was used as a base polymer, and a catechin polyphenol (SunphenonBG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (SunphenonBG-3)”) was used as a functional substance to make a non-woven fabric.

Zein and 20 wt % to 80 wt % of ethanol/water were mixed and the zein wasdissolved while heating (40° C. to 60° C.) to prepare zein solution. Inaddition, ethanol was added to the catechin (Sunphenon BG-3) and mixedto prepare a 20 wt % polyphenol compound-containing solution. Of the twosolutions, 7.5 g of zein-containing solution and 2.5 g of polyphenolcompound-containing solution were mixed to obtain a mixed solution. Thismixed solution was filled into a syringe. As a needle for a syringe, a25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, insidediameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied underatmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such away that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.29. An average fiber diameter of the non-woven fabric was 500 nm. Inaddition, a fiber with a diameter of 1 μm or larger was not observed. Aweight per unit area was 0.15 g/m². In addition, the weight per unitarea could be freely designed according to applications in a range of0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 20 Fibroin+Catechin Polyphenol

A fibroin was used as a base polymer, and a catechin polyphenol(Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin(Sunphenon BG-3)”) was used as a functional substance to make anon-woven fabric.

10 g of fibroin and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solutionwere mixed, and the fibroin was dissolved at normal temperature (about25° C.) to prepare a fibroin solution (polymer-containing solution). Inaddition, ethanol was added to the catechin (Sunphenon BG-3) and mixedto prepare a 20 wt % polyphenol compound-containing solution. Of the twosolutions, 7.5 g of fibroin-containing solution and 2.5 g of polyphenolcompound-containing solution were mixed to obtain a brown transparentmixed solution. This mixed solution (transparent solution containingfibroin and catechin polyphenol) was filled into a syringe. As a needlefor a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter:0.5 nm n, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KVwas applied under atmospheric pressure at room temperature (about 25°C.), and electrospinning was carried out in such a way that the distancefrom the inner bore on the syringe needle tip to the fibrousmaterial-collecting electrode was set to 10 cm to 200 cm to obtain thenanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.30 and FIG. 31. An average fiber diameter of the non-woven fabric was500 nm. In addition, a fiber with a diameter of 1 μm or larger was notobserved. A weight per unit area was 0.5 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 21 Nylon 6,6+Catechin Polyphenol

A nylon 6,6 was used as a base polymer, and a catechin polyphenol(Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin(Sunphenon BG-3)”) was used as a functional substance to make anon-woven fabric.

10 g of nylon 6,6 and 90 g of formic acid were mixed and the nylon 6,6was dissolved at normal temperature (about 25° C.) to prepare a nylon6,6-containing solution (polymer-containing solution). In addition,ethanol was added to the catechin (Sunphenon BG-3) and mixed to preparea 20 wt % polyphenol compound-containing solution (functionalsubstance-containing solution). Of the two solutions, 7.5 g of nylon6,6-containing solution and 2.5 g of polyphenol compound-containingsolution were mixed to obtain a brown transparent mixed solution. Thismixed solution (transparent solution containing nylon 6, 6 and catechinpolyphenol) was filled into a syringe. As a needle for a syringe, a 25 Gneedle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter:0.32 mm) was used. Voltage of 20 KV to 50 KV was applied underatmospheric pressure at room temperature (about 25° C.), andelectrospinning was carried out in such a way that the distance from theinner bore on the syringe needle tip to the fibrous material-collectingelectrode was set to 10 cm to 200 cm to obtain the nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.32 and FIG. 33. An average fiber diameter of the non-woven fabric was150 nm. In addition, a fiber with a diameter of 1 μm or larger was notobserved. A weight per unit area was 0.1 g/m². In addition, the weightper unit area could be freely designed according to applications in arange of 0.005 g/m² to 10 g/m² by appropriately changing the conditions.

Example 22 Three Layer-Reinforced Nanofiber (Non-Woven Fabric 4Polyurethane Nanofiber+Soluble Nylon Nanofiber+Catechin)

A commercially available non-woven fabric of 10 μm to 50 μm was used asa collector, polyurethane was used as a reinforcing nanofiber,methoxymethylated nylon was used as a base polymer and a catechinpolyphenol (Sunphenon BG-0.3, Taiyo Kagaku Co., Ltd., hereinafter called“catechin (Sunphenon BG-3)”) was used as a functional substance to makea non-woven fabric.

10 g of polyurethane and 90 g of dimethylformamide solution were mixedand the polyurethane was dissolved at normal temperature (about 25° C.)to prepare a polyurethane-containing solution (polymer-containingsolution). Subsequently, this solution was filled into a syringe. As aneedle for a syringe, a 2.5 g needle (HOSHISEIDO Co., Ltd., outsidediameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KVto 50 KV was applied under atmospheric pressure at room temperature(about 25° C.), and electrospinning was carried out in such a way thatthe distance from the inner bore on the syringe needle tip to thefibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the nanofiber non-woven fabric on a collector (a commerciallyavailable non-woven fabric).

Subsequently, 10 g of methoxymethylated nylon and 90 g of1,1,1,3,3,3-hexafluoroisopropanol (HFIP) were mixed andmethoxymethylated nylon was dissolved at normal temperature (about 25°C.) to prepare a methoxymethylated nylon-containing solution(polymer-containing solution). In addition, ethanol was added to thecatechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenolcompound-containing solution (functional substance-containing solution).Of the two solutions, 7.5 g of methoxymethylated nylon-containingsolution and 2.5 g of polyphenol compound-containing solution were mixedto obtain a brown transparent mixed solution. Then, this mixed solution(transparent solution containing the methoxymethlated nylon and catechinpolyphenol) was filled into a syringe. As a needle for a syringe, a 2.5g needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, insidediameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied underatmospheric pressure at room temperature (about 25° C.), and thecommercially available non-woven fabric+polyurethane nanofiber madeabove was used as a collector, on which electrospinning was carried outin such a way that the distance from the inner bore on the syringeneedle tip to the fibrous material-collecting electrode was set to 10 cmto 200 cm to obtain the three layer-reinforced nanofiber non-wovenfabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.34 and FIG. 35. Average fiber diameters of the obtainedcatechin-containing nanofiber non-woven fabrics were 500 nm in thepolyurethane nanofiber and 150 nm in the catechin+soluble nylonnanofiber. In addition, a fiber with a diameter of 1 μm or larger wasnot observed. The weight per unit area was 0.1 g/m². In addition, theweight per unit area could be freely designed according to applicationsin a range of 0.005 g/m² to 10 g/m² by appropriately changing theconditions.

Example 23 Three Layer-Reinforced Nanofiber (Non-WovenFabric+Polyurethane Nanofiber+Polyvinyl Alcohol Nanofiber+Catechin)

A commercially available non-woven fabric of 10 μm to 50 μm was used asa collector, polyurethane was used as a reinforcing nanofiber,methoxymethylated nylon was used as a base polymer and a catechinpolyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called“catechin (Sunphenon BG-3)”) was used as a functional substance to makea non-woven fabric.

10 g of polyurethane and 90 g of dimethylformamide solution were mixedand the polyurethane was dissolved at normal temperature (about 25° C.)to prepare a polyurethane-containing solution (polymer-containingsolution). Subsequently, this solution was filled into a syringe. As aneedle for a syringe, a 2.5 g needle (HOSHISEIDO Co., Ltd., outsidediameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KVto 50 KV was applied under atmospheric pressure at room temperature(about 25° C.), and electrospinning was carried out in such a way thatthe distance from the inner bore on the syringe needle tip to thefibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the nanofiber non-woven fabric on a collector (a commerciallyavailable non-woven fabric).

Subsequently, 10 g of polyvinyl alcohol and 90 g of water were mixed andmethoxymethylated nylon was dissolved at normal temperature (about 25°C.) to prepare a methoxymethylated nylon-containing solution(polymer-containing solution). In addition, ethanol was added to thecatechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenolcompound-containing solution (functional substance-containing solution).Of the two solutions, 7.5 g of polyvinyl alcohol-containing solution and2.5 g of polyphenol compound-containing solution were mixed to obtain abrown transparent mixed solution. Then, this mixed solution (transparentsolution containing the polyvinyl alcohol and catechin polyphenol) wasfilled into a syringe. As a needle for a syringe, a 2.5 g needle(HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32mm) was used. Voltage of 20 KV to 50 KV was applied under atmosphericpressure at room temperature (about 25° C.), and the commerciallyavailable non-woven fabric+polyurethane nanofiber made above was used asa collector, on which electrospinning was carried out in such a way thatthe distance from the inner bore on the syringe needle tip to thefibrous material-collecting electrode was set to 10 cm to 200 cm toobtain the three layer-reinforced nanofiber non-woven fabric.

Electron micrographs of the resulting non-woven fabric are shown in FIG.36 and FIG. 37. Average fiber diameters of the obtainedcatechin-containing nanofiber non-woven fabrics were 500 nm to 1000 nmin the polyurethane nanofiber and 250 nm in the catechin+polyvinylalcohol nanofiber. In addition, a fiber with a diameter of 1 μm orlarger was not observed. The weight per unit area was 0.1 g/m². Inaddition, the weight per unit area could be freely designed according toapplications in a range of 0.005 g/m² to 10 g/m² by appropriatelychanging the conditions.

Comparative Example 1

As a Comparative Example 1, the nanofiber in the Example 1 described inPatent Literature 4 was manufactured as below.

90 mg of polylactic acid (Weight-average molecular weight (Mw)=123,000,Number average molecular weight (Mn)=61,000, Trade name: LACEA(Registered Trademark) H-900 (Mitsui Chemicals, Inc.)) and 819 mg of1,1,1,3,3,3-hexafluoroisopropanol (HFIP) were added to a sample bottle,and the polylactic acid was completely dissolved while stirring by amagnetic stirrer at normal temperature (20° C. to 25° C.) overnight(about 10 hours or longer).

4.5 mg of epigallocatechin gallate (EGCg: Sunphenon EGCg, Taiyo KagakuCo., Ltd.) and 86.5 mg of dimethylformamide (DMF) were added to anothersample bottle, and the EGCg was completely dissolved while stirring bythe magnetic stirrer at normal temperature for 1 to 2 hours.

909 mg of polylactic acid solution and 91 mg of EGCg solution were mixedin yet another sample bottle and shaken and stirred by a vortex mixeruntil they were equalized. After being shaken and stirred, the solutionyielded a white turbidity.

The mixed solution of the polylactic acid and the EGCg was injected intoa syringe, and then air bubbles in the syringe were removed. Thissyringe was set to a syringe pump of an electrospinning device. As aneedle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outsidediameter: 0.5 mm, inside diameter: 0.32 mm) was used to carry outelectrospinning with an injection range of 10 cm, a rotating speed of100 rpm, a voltage of 10 kv and an injection speed of 3 mL/hr.

A nanofiber non-woven fabric having an outside diameter of about 100 nmto 500 nm was manufactured by the electrospinning method. However,insoluble matter of the EGCg in a nearly spherical shape was scatteredin spots on the nanofiber. It was considered that, because the EGCgsolution once dissolved was mixed with the polylactic acid solution, itthereby returned to the undissolved state in the mixed solution in thesyringe.

<Test 1> Measurement of Absorbance of Solution for ElectrospinningAbsorbances of the solutions for electrospinning used in the Examples 1and 2 and Comparative Example 1 were measured at 660 nm. The results areshown in Table 1.

TABLE 1 Control (ion-exchanged Comparative water) Example 1 Example 2Example 1 OD660nm 0.003 0.003 0.016 3.626

Since the absorbances of the solutions in the Examples 1 and 2 werenearly equivalent to that of the control, it was considered thatfunctional substances were dissolved in these solutions. Meanwhile, theliquid in the Comparative Example 1 visually yielded a white turbidityand had an absorbance of as high as 3 or more, suggesting the functionalsubstance was undissolved.

<Test 2> Comparison Among Diameters of Nanofibers

The diameters of the nanofibers manufactured in the Examples 1 and 2 andComparative Example 1 were measured. In the results, the averagediameter of the nanofibers in the Examples 1 and 2 was 500 nm, and thatin Comparative Example 1 was 20 μm. Thus, these Examples revealed that ananofiber with a thinner diameter could be provided.

<Test 3> Elution Test of Polyphenol from Nanofibers

The nanofibers manufactured in the Examples 1 and 2 and ComparativeExample 1 were used to evaluate whether polyphenol was eluted.

Test method: 0.292 g of each electrospinning composition was measuredoff, put into a beaker including 50 ml of ion-exchanged water, andstirred by a magnetic stirrer at 8 rpm for 24 hours. Then, the totalpolyphenol content in this solution was measured by a ferrous tartratemethod.

In the ferrous tartrate method, the content was calculated by convertingit into the amount of gallic acid using an ethyl gallate as a standardsolution (Reference: “Green Tea Polyphenol”, Functional materialeffective utilization technology series for dietary drinks and foods,No. 10). 5 mL of the sample was colored with 5 mL of ferrous tartratestandard solution, measured up to 25 mL with a phosphate buffer, and itsabsorbance was measured at 540 nm to calculate the total polyphenolcontent from a calibration curve by the ethyl gallate.

Preparation of the ferrous tartrate standard solution: 100 mg of ferroussulfate heptahydrate, 500 mg of potassium sodium tartrate (Rochellesalt) were adjusted up to 100 mL with distilled water.

Preparation of the phosphate buffer: 1/15 M of disodium hydrogenphosphate solution and 1/15 M of sodium dihydrogen phosphate solutionwere mixed and adjusted to pH 7.5.

The results are shown in Table 2.

TABLE 2 Comparative Example 1 Example 2 Example 1 Eluted TP (ppm) 24.6226.17 92.86 In the table, TP means “Total Polyphenol.”

The Comparative Example 1 revealed elution of 92.86 ppm. Meanwhile, theExamples 1 and 2 showed about a quarter of the elution amount in theComparative Example 1, suggesting that the nanofibers in the Examplescontained the polyphenol in a form where the polyphenol could be elutedwith more difficulty.

Test 4> Antimicrobials Test

A quantitative test (bacteria solution absorption method) was conductedaccording to JIS L 1902. In the method, 0.4 g of sample was put into avial, 0.2 ml of the test bacteria solution was inoculated and culturedat 37±1° C. for 18±1 hours, to which 20 ml of saline containing 0.2% ofnon-ionic surfactant was added, and the bacteria was washed out from thesample, then the number of bacteria in the washing liquid was counted bythe colony method or the ATP method.

Bacteriostatic activity value=log(viable bacteria count after beingcultured on the standard fabric)−log(viable bacteria count after beingcultured on the processed sample)

Antimicrobial effects: Antimicrobial and deodorant processing,Bacteriostatic activity value≧2.0

As a result, in the nanofiber non-woven fabric in the Example 1, thebacteriostatic activity value was higher than 5.7, suggesting strongantimicrobial activity.

<Test 5> Deodorization Test

(1) Deodorization Test

The nanofiber manufactured in the Example 1 was used to make a nanofibernon-woven fabric. This nanofiber non-woven fabric was used to carry outa deodorization test. First, 2.7 L of atmosphere, each including 100 ppmof odorous components, were prepared in each odor bag, to which 4×4 cmof nanofiber non-woven fabric was placed, and concentrations of theodorous components were measured after 0, 1, 2, 3 and 24 hours.Detecting tubes dedicated for each odorous component (GASTECCORPORATION) were used for measurement. The results are shown in Table3. The concentrations (ppm/g) represent amounts of deodorization.

TABLE 3 Elapsed Time Ammonia Methylmercaptan Acetaldehyde Formaldehyde(hour) (ppm/g) (ppm/g) (ppm/g) (ppm/g) 0 0 0 0 0 0.5 828 491 365 18,8011 1,034 491 474 23,679 2 1,182 450 511 32,038 3 1,190 409 547 58,537 242,300 532 1,313 68,293

(2) Heating Desorption Test

A heating desorption test was carried out as acetaldehyde andformaldehyde are likely to be desorbed from the adsorbate duringheating.

The nanofiber non-woven fabric used in (1) Deodorization test, whichadsorbed acetaldehyde and formaldehyde for 24 hours was placed into aodor bag containing 3 L of air, and a heating test was carried out underan atmosphere at 80° C. in an incubator to measure the gasconcentrations after 0, 1, 2 and 3 hours by a gas detecting tube.

The results are shown in Table 4. The concentrations (ppm/g) representamounts of desorption.

TABLE 4 Elapsed Acetaldehyde absorbed Formaldehyde absorbed Timenanofiber non-woven nanofiber non-woven (hour) fabric (ppm/g) fabric(ppm/g) 0 1 2 1 0 1 2 0 0 3 0 0

<Test 6> Collection Test of Particles of 3 μm or Larger: BacterialFiltration Efficiency (BFE) Test

The nanofiber non-woven fabric manufactured by the above-mentionedExamples was used to make the mask with functional material (surgicalmask), and the mask was used to carry out the BFE test.

Details of the test method were in accordance with the procedure set inASTM-F2101-07, specifically, as below.

When the bacteria was collected by Andersen sampler using Staphylococcusaureus ATCC 6538, a bacteria turbid solution was made so that the totalcolony count was 2200±500. 27 ml of agar medium was poured into eachschale for solidification.

The schales containing the agar medium were set to 1 to 6 racks of theAndersen sampler. Subsequently, the sample (15 cm×15 cm) was set betweenthe Andersen sampler and an aerosol chamber. The bacteria turbidsolution supplied from a bacteria turbid solution-supplying device to anebulizer was aerosolized by using a compressor so that the particlesize was about 3 μm, and sucked such that an airflow rate was 28.3L/minutes in the aerosol chamber and the Andersen sampler. Thisprocedure was performed for a certain period of time, then the schalesdrawn from the Andersen sampler were cultured at 37±2° C. for 48 hours.After being cultured, the number of colonies in the schales on the 1 to6 racks was counted. The BFE (%) was calculated by the followingformula.

$\begin{matrix}{{B\; F\; E} = {\frac{A - B}{A} \times 100(\%)}} & {{Formula}\mspace{14mu} 1}\end{matrix}$

In this formula, A represents the total colony count of the control, andB represents the total colony count when the sample was set.

As a result of this test, all of the masks showed 99% or more offiltration efficiency in the trapping performance for the fine particlesof 3 μm or larger.

<Test 7> Collection Test of Particles of 0.1 μm or Larger: ParticulateFiltration Efficiency Test

The nanofiber non-woven fabric manufactured by the above-mentionedExamples was used to make the mask with functional material (surgicalmask), and the mask was used to carry out the PFE test.

Details of the test method were in accordance with the procedure set inASTM F2299 (with the proviso that the particles were not neutralized),specifically, as below.

The test particles (0.1 μm polystyrene latex particle (JSR Corporation))were continuously supplied stably into the test chamber in which theenvironment was kept clean by a HEPA filter, the number of the particleson the front and back (upstream and downstream) of the filter materialas a test piece was counted by two particle counters during suction at aconstant flow rate, to calculate a collection efficiency (%).

The collection efficiency was calculated by the following formula.

PFE(%)=(1−downstream particle count/upstream particle count)×100

As a result of this test, all of the masks showed 99% or more offiltration efficiency in the trapping performance for the fine particlesof 0.1 μm or larger.

<Test 9> Antifungal Test

The nanofiber non-woven fabric manufactured by the above-mentionedExamples was used to make the mask with functional material (surgicalmask), and the mask was used to carry out the anti fungal test.

Details of the test method were in accordance with the procedure set inJIS Z 2911, specifically, as below.

As test fungus, Aspergillus niger ATCC 6275, Penicillium citrinum ATCC9849, Chaetomium globosum ATCC 6205, Myrothecium verrucaria ATCC 9095were respectively used, and an unglazed porcelain plate to which mixedtest fungus spores were bonded and dried was placed on a test piece (5×5cm) in a dry heat-sterilized schale, on which a glass plate was placed,covered with a lid, and cultured at 28±2° C. for 4 weeks to evaluategrowth statuses of mycelia.

As a result of this test, all of the masks showed no growth of mycelia.

<Test 10> Air Permeability Test

The test pieces obtained in the Examples 1 to 23 were measured by methodA (Frajour type method: set in JIS-L-1096) which is a testing method forgeneral fabric. In measurement, a surface to which the nanofiber did notadhere was brought into contact with a side of air suction.

Details of the test method were in accordance with the procedure set inJIS L 1096, specifically as below.

In this test, a Frajour type testing machine was used, and forpreparation, 200 mm×200 mm samples were respectively picked from 5different positions in a sample. The test piece was attached to acylindrical clamp (air suction port) of the Frajour type testingmachine. A suction fan was adjusted so that an inclined barometer was ata pressure of 125 Pa, and at the time of this adjustment, a pressure(cm) indicated in a vertical barometer was read. From the pressureindicated in the vertical barometer at the time of adjustment and thetype of used air orifice, an amount (cm³/cm²·sec) of air passing throughthe test piece was calculated by a conversion table attached to thetesting machine, and converted into the air permeability (cc/cm²·sec)below.

As a result of this test, all of the masks showed high air permeabilityof 100 or higher (cc/cm²·sec).

<Test 11> Wearing Test for Mask

(1) Making of Test Mask

Masks in which ready-made masks as bases were individually equipped withany one of the “non-woven fabric+nanofibers” shown in the Examples 2, 4,5, 6, 7, 8, 14, 16, 18 and 19 were made to carry out an evaluation testfor wearability of each mask. In the mask, a non-woven fabric of afilter part (hereinafter called a filter part) of a conventionalcommercially available mask was cut away leaving only one non-wovenfabric outside, to which this development article was applied instead ofthe cut filter and pressure-bonded into the same state as the initialstate by heating its surrounding area.

(2) Wearing Test for Mask

In the wearing test, first, 14 subjects (6 males: 2 in their 20s, 2 intheir 40s and 2 in their 50s; 8 females: 2 in their 20s, 2 in their 30s,2 in their 40s and 2 in their 50s) were given the test masks made asabove, which were randomly numbered in such a way that the ready-mademasks and the test masks could not be distinguished. Each subject worethe provided masks from No. 1 in turn, and they exchanged one mask afterthe next mask every one hour. Since there were 10 masks in all, 5 maskswere tested on each day for two days. In addition, between removal ofone mask and wearing of the next mask, the subject's breathing wasbrought back to normal by steadying the breathing once. After finishingwearing of the test masks No. 1 to No. 10 in this method, the meanvalues of evaluation results of all subjects were calculated. Theresults are shown in Table 5. In parallel, states of elimination andalleviation of oral odors were also evaluated on a scale of 1 to 5otherwise. The results are shown in Table 6.

TABLE 5 Results Example Example Example Example Example Example ExampleExample Example Example 2 4 5 6 7 8 14 16 18 19 Subjects A (20s, male) 45 5 4 3 5 5 4 2 4 B (20s, male) 3 4 4 4 4 5 4 4 3 3 C (40s, male) 5 4 44 3 5 4 4 3 3 D (40s, male) 4 5 5 3 4 5 5 3 2 3 E (50s, male) 3 5 5 3 45 5 4 2 3 F (50s, male) 3 4 5 4 3 4 5 4 3 3 G (20s, female) 3 5 5 4 4 54 3 3 5 H (20s, female) 3 4 4 4 4 4 4 3 3 3 I (30s, female) 4 4 4 4 3 54 3 3 3 J (30s, female) 3 5 4 3 3 5 5 3 3 3 K (40s, female) 3 5 4 4 4 53 4 3 3 L (40s, female) 3 5 4 3 3 4 5 4 3 3 M (50s, female) 5 5 4 3 4 54 4 3 3 N (50s, female) 3 4 4 4 3 4 4 3 3 3 Average 3.5 4.6 4.4 3.6 3.54.7 4.4 3.6 2.8 3.2

TABLE 6 Results Example Example Example Example Example Example ExampleExample Example Example 2 4 5 6 7 8 14 16 18 19 Subjects A (20s, male) 33 3 4 3 3 3 3 3 3 B (20s, male) 4 4 4 4 4 3 1 3 4 4 C (40s, male) 3 4 44 3 3 1 3 4 3 D (40s, male) 3 3 3 3 4 3 3 1 3 4 E (50s, male) 4 4 4 4 44 3 3 4 4 F (50s, male) 4 5 4 5 4 5 1 1 5 5 G (20s, female) 4 3 3 4 4 31 2 3 3 H (20s, female) 4 4 4 4 4 4 1 1 4 4 I (30s, female) 3 4 3 4 3 31 1 4 3 J (30s, female) 4 3 4 3 3 5 3 1 3 4 K (40s, female) 4 5 4 4 4 51 2 3 5 L (40s, female) 4 5 4 5 5 4 2 2 4 4 M (50s, female) 5 4 5 5 4 51 2 4 4 N (50s, female) 4 4 4 4 5 4 1 1 5 4 Average 3.8 3.9 3.8 4.1 3.93.9 1.6 1.9 3.8 3.9

As shown in these tables, according to the mask of this embodiment, themask having antioxidative effects, antimicrobial effects, antiviraleffects, deodorizing effect and the like as well as preferablewearability could be provided.

Thus, according to the Examples, a non-woven fabric containingfunctional substances uniformly on the surface of the nanofiber could bemanufactured. Since this nanofiber non-woven fabric has both functionsof the nanofiber and functions of catechins as the functionalsubstances, it has antioxidative effects, antimicrobial effects,antiviral effects, deodorizing effects, harmful substance-adsorbingeffects, antifungal effects and the like. Consequently, it can bepreferably used for a mask with functional material, particularly for asurgical mask.

1. A mask with a functional material which comprises a nanofibercontaining at least one base polymer selected from a group consisting ofPVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6,nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile,polyethylene terephthalate, polyvinyl chloride, polyurethane, polyester,zein, collagen and methoxymethylated nylon, and at least one functionalsubstance selected from a group consisting of catechin polyphenols,persimmon tannin polyphenols, grape seed polyphenols, soybeanpolyphenols, lemon peel polyphenols, coffee polyphenols,phenylcarboxylic acid, ellagic acid and coumalin, and having a diameterof 1 nm to 2000 nm.
 2. A mask with a functional material which comprisesnot only the nanofiber described in claim 1 but also a reinforcingnanofiber containing at least one reinforcing polymer selected from agroup consisting of PVA, polylactic acid, fibroin, chitosan, chitin,nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene,polyacrylonitrile, polyethylene terephthalate, polyvinyl chloride,polyester, zein, collagen and polyurethane and having a diameter of 1 nmto 2000 nm.
 3. The mask with the functional material according to claim1, wherein the functional substance is uniformly dispersed or dissolvedin the base polymer.
 4. The mask with the functional material accordingto claim 1 which consists of only the base polymer and the functionalsubstance.
 5. The mask with the functional material according to claim1, wherein a weight per unit area of the nanofiber is 0.005 g/m² to 10g/m².
 6. The mask with the functional material according to claim 1,wherein an air-permeability is 1 cc/cm²·sec to 1000 cc/cm²·sec.
 7. Themask with the functional material according to claim 1, wherein a resinconstituting the resin composition mask is negatively or positivelyelectrostatically-charged and attracts surrounding substances positivelyor negatively electrostatically-charged.
 8. The mask with the functionalmaterial according to claim 1 which is a surgical mask, wherein theresin composition mask is composed of a non-woven fabric and is forsurgical applications.
 9. The surgical mask according to claim 8,wherein a trapping performance for fine particles of 0.1 μm or larger is99% or more.
 10. The surgical mask according to claim 8, wherein atrapping performance for fine particles of 3 μm or larger is 99% ormore.
 11. A manufacturing method for the mask according to claim 1,wherein a polymer-containing solution is prepared by dissolving at leastone base polymer selected from a group consisting of PVA, polylacticacid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon610, polyamide, polystyrene, polyacrylonitrile, polyethyleneterephthalate, polyvinylidene chloride, polyester, zein, collagen,polyvinyl chloride, methoxymethylated nylon and polyurethane in at leastone solvent selected from a solvent group consisting of water, acetone,methanol, ethanol, propanol, toluene, benzene, cyclohexane,cyclohexanone, tetrahydrofuran, dimethylsulfoxide, 1,4-dioxane, carbontetrachloride, methylene chloride, pyridine, N-methyl-2-pyrrolidone,ethylene carbonate, diethyl carbonate, propylene carbonate,acetonitrile, lactic acid, acetic acid, dimethylacetamide,dimethylformamide, dichloromethane, trichloromethane,hexafluoroisopropanol, formic acid, chloroform, formaldehyde andacetaldehyde; a functional substance-containing solution is prepared bydissolving at least one functional substance selected from a groupconsisting of catechin polyphenols, persimmon tannin polyphenols, grapeseed polyphenols, soybean polyphenols, lemon peel polyphenols, coffeepolyphenols, phenylcarboxylic acid, ellagic acid and coumalin in atleast one solvent selected from the solvent group; a mixed solution isprepared by mixing the polymer-containing solution and the functionalsubstance-containing solution; and the mask is manufactured from a fibermade by spinning this mixed solution by an electrospinning method. 12.The manufacturing method for the mask according to claim 11, wherein anyof the solvents for preparing the polymer-containing solution and thefunctional substance-containing solution is any one selected from agroup consisting of formic acid, hexafluoroisopropanol, water,dimethylformamide, ethanol and dichloromethane.
 13. The manufacturingmethod for the mask according to claim 11, wherein the functionalsubstance-containing solution contains sodium chloride.
 14. Themanufacturing method for the mask according to claim 11, wherein themixed solution is uniform in properties and transparent.